CN1884364B - Composition for manufacturing photochromic resin lens - Google Patents

Abstract

The invention relates to a composition for manufacturing photochromic resin lenses. 1. Add antioxidants, hindered amines, ultraviolet absorbers, light stabilizers, polymerization regulators, etc. to the monomer mixture to increase the lifespan of photochromic dyes. 2. Adding an internal plasticizer to the monomer mixture greatly improves the impact resistance of the lens. 3. Adding epoxy and amine-based monomers greatly improves the film fastness of the lens.

Description

A kind of composition for making photochromic resin lens

technical field

The invention relates to a composition for making lenses, in particular to a composition for making photochromic resin lenses.

Background technique

Glasses are a kind of widely used, necessary articles for people's daily life, eyeglasses are the key parts of glasses, the quality of its performance will directly affect the use effect of glasses.

The current ordinary acrylic lens material is relatively brittle and cannot be drilled into wires, so it is not suitable for making rimless glasses. Commercial photochromic lenses have a short service life, generally no more than three years. The step of carrying out special pretreatment not only has high processing cost, but also the quality of the lens is poor, and the transmittance of the lens to ultraviolet light below 400 nanometers is lower than 2.5%. The impact strength of the lens after molding is low, and the toughness of the lens cannot meet people's needs.

Contents of the invention

The technical problem to be solved in the present invention is to disclose a composition for manufacturing photochromic resin lenses, so as to overcome the above-mentioned defects in the prior art.

The components and weight percent content of the composition for making photochromic resin lenses of the present invention include:

(1) Monomer mixture:

(meth)acrylic resin 40-69%

Styrene 20-40%

Internal plasticizer 5-10%

Polymerization regulator 1-3%

Amino monomer 3-5%

Epoxy monomer 2-5%

(2) The amount of auxiliary materials in one kilogram of monomer mixture:

Color-changing dye 0.2-0.6 grams

Initiator 1-2.5 grams

Antioxidants and hindered amines 3-6 grams

UV absorber 0.05-0.2g

Light stabilizer 2-5 grams

Said (meth)acrylic resin is selected from methyl (meth)acrylate, ethyl acrylate, cyclohexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl acrylate , Isobornyl (meth)acrylic acid, α-bromoethyl acrylate, α-chloroethyl acrylate, chloromethyl (meth)acrylate, 2-bromoethyl (meth)acrylate, (meth)acrylic acid 2-naphthyl ester, p-cresyl acrylate, p-chlorophenyl (meth)acrylate, m-bromophenyl acrylate, 2,4,6-tribromophenyl acrylate, p-chlorobenzyl (meth)acrylate, (meth) base) m-methoxybenzyl acrylate, p-ethylbenzyl acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol diacrylate, thiodiglycol di(meth)acrylate Alcohol Esters, Ethoxylated Bisphenol A Diacrylate, Ethoxylated Bisphenol A Di(meth)acrylate, Pentaerythritol Triacrylate, Glycerin Triacrylate, Trihydroxy(methyl)propane Triethoxylated Tris Hydroxy(meth)propane tri(meth)acrylate, Tripropylene glycol diacrylate, Polyethylene glycol (200) (meth)diacrylate, Polyethylene glycol (400) (meth)diacrylate, Polyethylene Glycol (600) (Meth) Diacrylate, Tris (2-Hydroxyethyl) Isocyanurate Tri (Meth) Acrylate, Tris Hydroxyl (Meth) Propane Polyoxyethylene Triacrylate, Urethane acrylate, urethane (meth)acrylate, bis[4-(meth)acryloylthiophenyl]sulfide, pentaerythritol tetrapropionate, ethoxylated pentaerythritol tetra Acrylate, bis-trihydroxy(methyl)propane tetraacrylate, propoxylated pentaerythritol tetraacrylate or a mixture of two or more of pentaerythritol tetraacrylate;

Said internal plasticizer is selected from dibutyl maleate or dioctyl maleate;

The polymerization regulator is selected from methyl bromide or dodecyl mercaptan;

The amino monomer is selected from urethane acrylate or urethane (meth)acrylate;

The epoxy monomer is selected from epoxy acrylate or epoxy (meth)acrylate;

The color-shifting dye is selected from helical naphthoxazines or naphthopyrans;

The initiator is selected from azobisisoheptanonitrile or azobisisobutyronitrile;

The antioxidant is selected from the group consisting of tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid]pentapentaerythyl alcohol, β(3,5-di-tert-butyl-4-methylphenol, 1,3,5-tri(methyl)-2,4,6-tri(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 1,3,5-tri(3,5-di tert-butyl-4-hydroxybenzyl) isocyanate or 2,4,6-tri-tert-butylphenol;

The hindered amine is selected from bis(2,2,6,6-tetramethyl-4-piperidine) sebacate or succinic acid and (4-hydroxy-2,2,6,6-tetramethyl-1 - piperidine ethanol) polymer;

The UV absorber is selected from 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-cyano-3-methyl(p-methoxyphenyl)methyl acrylate, 2-cyano -3-methyl-3-(p-methoxyphenyl)methyl acrylate, 2-(3'-tert-butyl-2'-hydroxy-5'-methylpropyl)-5-chlorobenzo Triazole, 2-(3′,5′-di-t-pentylphenyl)benzotriazole, (2-hydroxy-5-tert-octylphenol)benzotriazole or 2-hydroxy-4-n-octyloxy Benzophenone;

The light stabilizer is selected from multifunctional penta(methyl) piperidine esters, poly(methyl) polymerized piperidines, bis(2,2',6,6'-tetramethylpiperidine) sebacate, 4 -Benzoyl-2,2',6,6'-tetramethylpiperidine, bis(1,2,2',6,6'-pentamethyl-4-piperidinyl) sebacate Or 4-(p-toluenesulfonamido)-2,2',6,6'-tetra(methyl)piperidine;

The method for preparing a photochromic resin lens using the composition of the present invention comprises the following steps:

The above composition is filtered with a 0.5 micron filter and poured into a pre-prepared glass mold, and the poured mold is put into an oven for polymerization according to the following heating procedure:

1. Room temperature---43℃ for 0.5 hours

2. 43℃---43℃ for 8 hours

3. 43℃---55℃ for 6 hours

4. 55℃---85℃ for 4 hours

5. 85℃---85℃ for 2 hours

6. 85℃---60℃ for 1.5 hours

The photochromic resin lens can be obtained by removing the glass mold at 60°C.

The new photochromic lens raw material formula and its simple lens manufacturing method can obtain good use function of the lens. It is characterized in that in addition to general (meth)acrylate monomers, a highly functional component is added to the raw material formula:

Epoxy resin monomers and amine-based monomers not only greatly improve the impact strength of the lens after molding, but also greatly improve the toughness of the lens, which can be used to prepare rimless glasses; at the same time, this improvement also makes the coating post-treatment process of the lens It becomes very simple, which not only saves the cost of coating processing, but also improves the fastness of the film layer and improves the performance of the lens.

The composition of acrylic monomers can be adjusted flexibly, and optical lenses with different refractive indices can be obtained conveniently.

Adding hindered amines, antioxidants, and anti-ultraviolet absorbers and ingenious combination can obtain a long service life of the lens.

Adding a polymerization regulator can make the free radical polymerization process easy to control, and the qualified rate of molding can be as high as 98%.

The photochromic resin lens prepared by the composition of the present invention has the following excellent properties:

The refractive index of the lens can be adjusted between 1.53 and 1.58 according to customer requirements. The original light transmittance of the lens in the transparent state is greater than or equal to 86%, and the light transmittance can be reduced to 21% after being irradiated by ultraviolet rays or sunlight, thus achieving the purpose of multi-purpose mirror. That is to say, the lens can be used not only for vision correction of eyes, but also for sunglasses, and meanwhile, it can also prevent electromagnetic waves.

The impact strength of the lens can be as high as 60KJ/m ² , and when the lens is drilled with a drilling machine, the drilled resin chips can be continuously formed into filaments. This kind of lens can be used for assembling rimless glasses, which overcomes the disadvantages that the ordinary acrylic lens material is brittle and cannot be drilled into threads, so it is not suitable for assembling rimless glasses.

The service life of the lens is very long, and the service life of the discoloration agent contained in it can reach more than three years under normal use, which reaches or exceeds the service life of the lens material itself.

This kind of photochromic lens can be processed by using conventional resin lens with hard film and anti-reflection film process, and the fastness of the film layer can reach the first-class standard, thus eliminating the need for special pretreatment before adding film to general photochromic lens The steps save the processing cost and improve the quality of the lens.

The transmittance of the lens to ultraviolet light below 400 nanometers is less than 2.5%.

Detailed ways

Example 1

Recipe: (weight)

Ethoxylated bisphenol A di(meth)acrylate 150g

Polyethylene glycol (200) di(meth)acrylate 50g

Pentaerythritol Tripropenyl 280g

Styrene 330 g

Dibutyl maleate 80g

Aminoacrylate 50g

Epoxy acrylate 40 grams

Methyl bromide 20 grams

1,2-b naphthopyran (Berry Red by James Robinson, UK) 0.2 g

Azobisisoheptanonitrile 1.5 g

Azobisisobutyronitrile 0.5 g

β(3,5-Di-tert-butyl-4-hydroxyphenyl) octadecyl propionate 2 grams

Succinic acid and (4-hydroxy-2,26,6,-tetramethyl-1-piperidineethanol) polymer 2 g

(2-Hydroxy-5-tert-octylphenyl ester)benzotriazole 0.1 g

Bis(2,2′,6,6′-tetramethylpiperidine) sebacate 2 grams Preparation method: filter the above composition with a 0.5 micron filter and pour it into a pre-prepared glass mold, pour Put the good mold into the oven to carry out the polymerization reaction according to the following heating procedure:

1. Room temperature---43℃ for 0.5 hours

2. 43℃---43℃ for 8 hours

3. 43℃---55℃ for 6 hours

4. 55℃---85℃ for 4 hours

5. 85℃---85℃ for 2 hours

6. 85℃---60℃ for 1.5 hours

The photochromic resin lens can be obtained by removing the glass mold at 60°C.

The prepared lenses were tested using the methods stipulated in ISO8980.3-1999 "Raw Edge Spectacle Lenses Part III: Requirements and Test Methods for Transmission Properties" and QB2506-2001 "Optical Resin Spectacle Lenses", and the results are as follows:

1. Visible light original transmittance: 89%

2. UV transmittance: 2.4%

3. Transmittance in 15 minutes (500nm): 30%

4. Impact resistance performance Passed QB2506 regulations

Example 2

Ethoxylated bisphenol A di(meth)acrylate 450g

1,6-butylene diester acrylate 80 grams

Ethoxylated trihydroxy(methyl)propane triacrylate 120g

Aminoacrylate 30g

Lauryl Mercaptan 20g

Styrene 25 g

Dioctyl maleate 5 g

1,2-b naphthoxazine (Velvet Blue by James Robinson, UK) 0.4 g

2,4,6-tri-tert-butylphenol 5 grams

Bis(2,2,6,6-tetramethyl-piperidine) sebacate 3 grams

2-Hydroxy-4-n-octyloxybenzhydryl ester 0.15g

4-methylbenzoyl-2,2′,6,6′-tetra(methyl)piperidine 3 grams

Preparation method: filter the above composition with a 0.5 micron filter and pour it into a pre-prepared glass mold, put the cast mold into an oven and carry out the polymerization reaction according to the following heating procedure:

1. Room temperature---43℃ for 0.5 hours

2. 43℃---43℃ for 8 hours

3. 43℃---55℃ for 6 hours

4. 55℃---85℃ for 4 hours

5. 85℃---85℃ for 2 hours

6. 85℃---60℃ for 1.5 hours

The photochromic resin lens can be obtained by removing the glass mold at 60°C.

The prepared lenses were tested using the methods stipulated in ISO8980.3-1999 "Raw Edge Spectacle Lenses Part III: Requirements and Test Methods for Transmission Properties" and QB2506-2001 "Optical Resin Spectacle Lenses", and the results are as follows:

1. The original light transmittance: 90%

2. UV transmittance: 2.5%

3. 15-minute transmittance (605 nm): 35%

4. Impact resistance passed QB2506

Claims (9)

1. A composition for making photochromic resin lens, it is characterized in that, component and weight percent content comprise: (1) Monomer mixture: (meth)acrylate 40-69% Styrene 20-40% Internal plasticizer 5-10% Polymerization regulator 1-3% Amino monomer 3-5% Epoxy monomer 2-5% (2) The amount of auxiliary materials in one kilogram of monomer mixture: Color-changing dye 0.2-0.6 grams Initiator 1-2.5 grams Antioxidants and hindered amines 3-6 grams UV absorber 0.05-0.2g Light stabilizer 2-5 grams The hindered amine is selected from bis(2,2,6,6-tetramethyl-4-piperidine) sebacate or succinic acid and (4-hydroxyl-2,2,6,6-tetramethyl -1-piperidineethanol) polymer; The ultraviolet absorber is selected from 2-(2'-hydroxyl-5'-methylphenyl) benzotriazole, 2-(3', 5'-dipentylphenyl) benzotriazole or 2 -Hydroxy-4-n-octyloxybenzophenone; The photostabilizer is selected from polyfunctional penta(methyl) piperidine esters, 4-benzoic acid group-2,2',6,6'-tetramethylpiperidine or 4-(p-toluenesulfonamide )-2,2',6,6'-tetra(methyl)piperidine. 2. composition according to claim 1, is characterized in that, said (meth)acrylate is selected from methyl (meth)acrylate, ethyl acrylate, (meth)cyclohexyl acrylate, (meth)acrylate Base) 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, α-chloroethyl acrylate, chloromethyl (meth)acrylate, 2-bromoethyl (meth)acrylate, 2-(meth)acrylate Naphthyl esters, p-cresyl acrylate, p-chlorophenyl (meth)acrylate, m-bromophenyl acrylate, 2,4,6-tribromophenyl acrylate, p-chlorobenzyl (meth)acrylate, (meth) m-methoxybenzyl acrylate, p-ethylbenzyl acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol diacrylate, thiodiethylene glycol di(meth)acrylate , ethoxylated bisphenol A diacrylate, pentaerythritol triacrylate, glycerol triacrylate, trihydroxy(meth)propane polyoxyethylene triacrylate, ethoxylated pentaerythritol tetraacrylate, propoxylated pentaerythritol tetraacrylate or A mixture of two or more types of pentaerythritol tetraacrylate. 3. The composition according to claim 2, characterized in that said internal plasticizer is selected from dibutyl maleate or dioctyl maleate. 4. The composition according to claim 3, characterized in that the polymerization modifier is selected from methyl bromide or dodecyl mercaptan. 5. Composition according to claim 4, characterized in that the amine-based monomer is selected from urethane (meth)acrylates. 6. The composition according to claim 5, wherein the epoxy monomer is selected from epoxy (meth)acrylates. 7. Composition according to claim 6, characterized in that the color changing dye is selected from the group consisting of spironaphthoxazines or naphthopyrans. 8. The composition according to claim 7, wherein the initiator is selected from azobisisoheptanonitrile. 9. The composition according to claim 8, wherein the antioxidant is selected from tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid] pentaerythritol, 1,3, 5-tris(methyl)-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene or 2,4,6-tri-tert-butylphenol.